Metal Hexacarbonyls Research Articles

Synthesis of [(CO)5MS=CFcCH3] and exploration of the nature of M-S vs. M-O bonds in [(CO)5ME=CFcCH3]; (M = Cr, Mo, W and E = O, S) complexes

Photolysis of a methanol solution containing substituted alkyne, group VI metal hexacarbonyl and P4S10 at low temperature under an inert atmosphere leads to metal-sulfur coordinated complexes of chromium, molybdenum, and tungsten. The structure of pentacarbonylthioacetylferrocene-S-chromium (1) is confirmed by single crystal x-ray diffraction study and both the complexes (1 and 2) are confirmed using IR and NMR spectral studies. The sulfur-coordinated metal carbonyl complexes are thought to be formed by the initial activation of metal carbonyl with acetylenic ligand which then rearranges into metal coordinated thioacetylferrocene by dithiophosphoryl radical (formed in situ by reaction of P4S10 and methyl alcohol under photolytic condition). The stability of pentacarbonylthioacetylferrocene of group VI metal complexes are further compared with their acetylferrocene derivatives of Group VI metal complexes using DFT studies. Density functional theory was performed on six complexes [(CO)5ME=CFcCH3] (where M = Cr, Mo and W; while E = O and S) to assess their geometry and electronic structure aspects. Natural bonding orbital (NBO) and energy-decomposition analysis (EDA) were carried out to probe the nature and strength of the M-E interactions. NBO and EDA analysis predict M-E bond strength in the following order: Cr-E < Mo-E < W-E. The M-E bond covalency increases as we move down the group from Cr, Mo to W, which rationalizes the observed trends in the M-E bonds. While comparing the nature of the E (O and S) linkage in bonding, we found that -S analogue shows exceptionally robust σ and π interactions compared to the -O analogue. The reasonably strong M-S interactions resulted in the isolation of these -thio analogues.

Tetracarbonyl group 6B metal complexes of a N-(4-acetylphenyl)-N-(diphenylphosphino)amine ligand. Molecular structure of cis-[Cr(CO)4{4-CH3CO–C6H4-1-N(PPh2)2}]

Chemical reactions of N-(4-acetylphenyl)-N-(diphenylphosphino)amine ligand (1) with three group 6B metal hexacarbonyls produced cis-M(CO)4[1-k2P,P][ M = Cr(2), Mo(3), W(4)], respectively. The novel complexes 2–4 were isolated and their structures were elucidated by multinuclear NMR spectroscopy (1H, 13C, 31P NMR) and elemental analysis. Crystal-structure determination using single-crystal X-ray diffraction was carried out on complex 2.

Zero-valent metals in metal-organic frameworks: fac-M(CO)3(pyrazine)3/2.

We report the synthesis of pyrazine-pillared metal-organic frameworks (MOFs) generated through ligand substitution of the Group 6 metal hexacarbonyls. The obtained frameworks exhibit hexagonal pore channels with CO-plastered porewalls. This series constitutes the first crystallographically characterized examples of Cr(0), Mo(0), and W(0)-based MOFs and suggests the exploration of homoleptic metal carbonyls as starting materials to generate polymeric materials with low-valent metal nodes.

Tetracarbonyl &lt;i&gt;N&lt;/i&gt;-(4-Acetylphenyl)- &lt;i&gt;N&lt;/i&gt;-(Diphenylphosphino)- &lt;i&gt;P,P&lt;/i&gt;-Diphenylphosphinous Amide Complexes of Group 6B Metals - Molecular Structure of &lt;i&gt;cis&lt;/i&gt;-[Cr(CO) &lt;sub&gt;4&lt;/sub&gt;{4-CH &lt;sub&gt;3&lt;/sub&gt;CO-C &lt;sub&gt;6&lt;/sub&gt;H &lt;sub&gt;4&lt;/sub&gt;-1-N(PPh &lt;sub&gt;2&lt;/sub&gt;) &lt;sub&gt;2&lt;/sub&gt;}

The reaction of p-aminoacetophenone [(p-CH3CO)C6H4NH2] with two equivalents of chlorodiphenylphosphine (Ph2PCl) gave the ligand (p-CH3CO)C6H4N(PPh2)2 (1) in good yield. Reactions of 1 with group 6B metal hexacarbonyls afforded cis-M(CO)4[1-k2P,P][M = Cr(2), Mo(3), W(4)], respectively. Complexes 2-4 were identified and characterized by multinuclear NMR spectroscopy (1H, 13C, 31P NMR) and elemental analysis. Crystal-structure determination is carried out on complex 2.

(Invited) Wafer-Scale Epitaxy of Transition Metal Dichalcogenides By MOCVD

Monolayer semiconducting transition metal dichalcogenides (MX2, M=W, Mo and X=S, Se) exhibit novel electronic and optical properties. Availability of epitaxial single-crystal monolayers over a wafer scale is a major hurdle in integrating these materials with existing device fabrication processes. Our approach focusses on synthesis of these monolayers using gas source precursors, like those used in traditional III-V semiconductor industry. The precursors are kept in temperature and pressure-controlled bubblers outside the growth chamber and can be metered independently into the growth zone with precision. Uniform epitaxial binary TMD monolayers including MoS2, WS2, WSe2 and MoSe2 have been deposited on 2” sapphire wafers in a cold-wall CVD reactor using metal hexacarbonyl and hydride chalcogen precursors. A multi-step growth process comprising of precursor modulation was developed for WSe2 to independently control nucleation density and the lateral growth rate of monolayer domains on the sapphire substrate [1]. For the sulfides, additional temperature modulation was introduced to increase crystalline quality. Using this approach, uniform, coalesced monolayer and few-layer TMD films were obtained on 2” sapphire substrates. In-plane X-ray diffraction demonstrates that the films are epitaxially oriented with respect to sapphire with narrow X-ray full-width-at-half-maximum indicating minimal rotational misorientation of domains within the basal plane [2]. Deposition of these materials in the same reactor provides insight into the factors controlling their growth, which in essential for the growth of heterostructures and/or alloys. Transmission electron microscopy analysis of these materials revealed additional information about the coalesced film structure. For instance, ~95 % single oriented WS2 domains were observed when the film growth rate was modulated. For WS2, it was also confirmed that despite translational line defects present in the film, mirror boundaries were predominantly absent. WS2 also showed no defect related photoluminescence peak at 80 K, indicating its high quality.In this talk the factors affecting the growth of TMDs (MX2, M=W, Mo and X=S, Se) will be presented. The role of the substrate surface in the nucleation and growth of these TMDs will be discussed. In addition, the structural and optoelectronic characteristics for these films will also be presented.The authors acknowledge financial support of the U.S. National Science Foundation through the Penn State 2D Crystal Consortium – Materials Innovation Platform (2DCC-MIP) under NSF cooperative agreement DMR-1539916 and EFRI 2-DARE Grant EFRI-1433378.[1] Zhang X, Choudhury TH, Chubarov M et al., 2018. Nano Lett. 18(2):1049–56[2] Chubarov M, Choudhury TH, Zhang X et al., 2018. Nanotechnology. 29(5):55706

Hydroconversion of 2-methylnaphtalene and dibenzothiophene over sulfide catalysts in the presence of water under CO pressure

Unsupported highly dispersed nanosized catalysts based on transition metal sulfides were prepared insitu, in water-oil emulsions, by high-temperature decomposition of oil soluble metal precursors using elemental sulfur as sulfiding agent. Their catalytic activity was tested in hydroconversion of 2-methylnaphtalene and dibenzothiophene at 380 °C under H2 pressure of 5 MPa. In addition, the catalysts were tested in the same reactions in the CO−H2O medium (p(CO) = 5 MPa, the CO: H2O molar ratio was 2: 1, ω(H2O) = 20 wt.%) in which hydrogen is formed through a water gas shift reaction (WGSR). Unsupported Ni−Mo-sulfide catalysts were found to be the most active compared to catalysts supported on alumina. Transmission electron microscopy served to investigate the structure and determine general geometric characteristics of Ni−Mo−S particles formed in toluene—water medium by decomposition of transition metal naphthenates and hexacarbonyls in the presence of elemental sulfur under CO pressure. The method described in this study enables one to synthesize nanosized catalysts with a high content of active sulfide phase.

Multiply charged energetic metal ion emissions from dinuclear metal complex exposed to intense femtosecond laser fields

Coulomb explosion of nonmetal ions emerged from a variety of molecules has been studied and utilized for the determination of molecular structure and reaction dynamics. In contrast, Coulomb explosion of metal ions, particularly the large Coulombic interactions are expected, has not yet been explored. In this study, the angular distributions of Mnx+ (x = 1–5), Cy+ (y = 1–4), and Oz+ (z = 1–3) emerged from dimanganese decacarbonyl, in which two metal atoms are sandwiched by axial ligands, exposed to intense femtosecond laser fields (1 × 1014–3 × 1015 W cm−2) are investigated. Manganese ions are produced at relatively low laser intensity compared with other transition metal ions with the same charge number but emerged from mononuclear complexes such as metallocenes and metal hexacarbonyls. The kinetic energies of Mn4+ and Mn5+ are described by the simple Coulomb repulsion model of manganese dimer ion. Fairly high kinetic energy of oxygen and carbon ions compared with those emerged from metal hexacarbonyls strongly suggests that atomic ions originating in ligands are repelled by manganese ions at the moment of Coulomb explosion. The use of dinuclear metal complex is advantageous in the production of multiply charged metal ions accompanying high kinetic energy since two manganese ions are in close confinement due to the repulsions with axial ligand (atomic) ions.

(Invited) The Role of Defects in Van Der Waals Epitaxy of Transition Metal Dichalcogenides

Direct growth of transition metal dichalcogenides (TMDs) such as WS2 and WSe2 on graphene and hexagonal boron nitride (hBN) is of interest for the fabrication of 2D heterostructures as an alternative to exfoliation and 2D layer stacking. This can be challenging, however, given the low surface energy of the basal plane in 2D layered materials which inhibits nucleation and lateral growth of TMD domains. In addition, it is equally probable for TMD domains to orient in two rotational directions (referred to as 0o and 180o domains) on pristine surfaces of hBN and graphene which gives rise to inversion domain boundaries (IDBs) in coalesced films. However, the presence of defects in hBN and graphene can dramatically alter the energy landscape providing a route to control nucleation and epitaxy. Our recent studies have focused on the epitaxial growth of WSe2, WS2 and related TMD monolayer films by gas source chemical vapor deposition (CVD) on hBN and epitaxial graphene. The CVD process is carried out in a cold-wall reactor using metal hexacarbonyls and hydride chalcogen precursors in a hydrogen carrier gas. In the case of epitaxial graphene, nucleation of WS2 occurs primarily at step edges and terrace defects resulting in different WS2 rotational orientations. In the case of WSe2 growth on hBN, however, single atom vacancies in the hBN were found to act as sites for metal atom trapping which facilitates the nucleation of WSe2 domains on the surface. In this case, the TMD nucleation density can be controlled by manipulating the density of surface atom vacancies which can be achieved through plasma irradiation and annealing in NH3. In addition, the metal atoms break the surface symmetry which leads to a preferred orientation (~95%) for WSe2 domains on hBN. Through careful control of nucleation and extended lateral growth time, fully coalesced WSe2 monolayer films on hBN were achieved which exhibit optical and transport properties superior to comparable films grown on sapphire substrates. The results demonstrate the important role of defects in nucleation and epitaxial growth of 2D heterostructures.

Synthesis of Dimethyl Phenylphosphonates Catalyzed by Group VI Metal(0) Hexacarbonyls

The coupling of dimethyl phosphite and iodobenzene occurs in the presence of catalytic amounts of homoligand carbonyl complexes of chromium subgroup metals to form dimethyl phenylphosphonate in yields of 50–73% depending on the metal.

Stabilization of Hydroxy Tautomeric Form of Dimethyl Phosphite in the Coordination Sphere of Carbonyl Complexes of Group VI Metals

The interaction of dimethyl phosphite with hexacarbonyls of the chromium group metals in a nonpolar solvent has afforded metal(0) σ4,λ4-(dimethyl phosphite)pentacarbonyls containing a hydroxy tautomeric form of dimethyl phosphite in the coordination sphere. Hydrogen of the phosphite OH group in the metal(0) σ4,λ4-(dimethyl phosphite)pentacarbonyls exhibited a significant acidity, strongest for the chromium complexes. Due to the significant acidity of the phosphite hydroxyl, the metal(0) σ4,λ4-(dimethyl phosphite)-pentacarbonyls are intermediates in the electrophilic version of the Pudovik reaction.

(Invited) Epitaxial Growth of 2D Transition Metal Dichalcogenide Monolayers, Alloys and Heterostructures

Two-dimensional (2D) transition metal dichalcogenides (TMDs) comprise a compelling class of new materials with intriguing properties that arise from their ultra-thin form, thickness-dependent bandstructure, large exciton binding energies and unusual spin and valley polarization physics. The majority of the research that has been carried out thus far employs ultra-thin TMD flakes exfoliated from bulk crystals but future device development requires the ability to synthesize large area single crystal films and heterostructures. Our research is aimed at the development of an epitaxial growth technology for TMDs and related layered chalcogenides based on gas source/metalorganic chemical vapor deposition (CVD/MOCVD) to enable monolayer growth over large substrate areas and layer-by-layer growth of heterostructures. Our recent studies have focused on the epitaxial growth of WSe2 and (Mo,W)S2 monolayer films, alloys and heterostructures using metal hexacarbonyl and hydride chalcogen precursors on substrates including sapphire and hexagonal boron nitride (hBN). A multi-step precursor modulation growth method was developed to independently control nucleation density and the lateral growth rate of TMD domains on the substrate. This approach also enables an estimation of metal-species surface diffusivity and domain growth rate as a function of growth conditions providing insight into the fundamental mechanisms of monolayer growth. Using the multi-step growth process, coalesced monolayer and few-layer TMD films were obtained on sapphire substrates up to 2” in diameter at growth rates on the order of ~ 1 monolayer/hour. In-plane X-ray diffraction demonstrates that the films are epitaxially oriented with respect to the sapphire resulting from a merging of 0o and 60o oriented domains. Room temperature photoluminescence (PL) measurements demonstrate strong emission peaks in the range of ~1.6 eV for WSe2 and ~2.0 eV for WS2 monolayers with lateral variations that may arise from residual strain in the films. (Mo,W)S2 alloy growth using simultaneous flows of Mo and W hexacarbonyl precursors reveals evidence of atomic scale ordering of Mo and W atoms within the monolayer. Growth and characterization of MoS2/WS2 and WSe2/WS2 vertical heterostructures will also be discussed.

(Invited) Epitaxy of 2D Transition Metal Dichalcogenide Monolayers and Heterostructures

There is growing interest in monolayer transition metal dichalcogenides (TMDs) such as MoS2 and WSe2 and related 2D heterostructures due to their compelling electronic and photonic properties. The majority of this work has been carried out using ultra-thin flakes exfoliated from bulk chalcogenide crystals but future device development requires the ability to synthesize large area single crystal films and heterostructures. Our research is aimed at the development of an epitaxial growth technology for layered dichalcogenides, similar to that which exists for III-V and other compound semiconductors, based on gas source chemical vapor deposition (CVD). This approach provides a high overpressure of chalcogen species needed to maintain stable growth at elevated temperature and excellent control of the precursor partial pressures to achieve layer-by-layer and heterostructure growth. Our recent studies have focused on the epitaxial growth of WSe2 and WS2 monolayer films and heterostructures using metal hexacarbonyl and hydride chalcogen precursors on substrates including sapphire and hexagonal boron nitride (hBN). A multi-step precursor modulation growth method was developed to independently control nucleation density and the lateral growth rate of WSe2 and WS2 monolayer domains on the substrate. This approach also enables measurement of W-species surface diffusivity and domain growth rate as a function of growth conditions providing insight into the fundamental mechanisms of monolayer growth. Using this approach, coalesced monolayer and few-layer TMD films were obtained on sapphire substrates up to 2” in diameter at growth rates on the order of ~ 1 monolayer/hour. In-plane X-ray diffraction demonstrates that the films are epitaxially oriented with respect to the sapphire resulting from a merging of an equal mixture of 0o and 60o oriented domains. WSe2 also grows epitaxially on hBN single crystal flakes but in this case the domains exhibit a predominant direction resulting in a reduced density of anti-phase boundaries. Applications and challenges of this approach in the growth of 2D heterostructures will also be discussed.

Synthesis, Chemical Characterization, and Biological Screening for Cytotoxic and Antitumor Activityof Novel p-Chlorophenyl Maleanilic Acid and Its Corresponding Chelates

A novel p-chlorophenyl maleanilic acid ligand (L) was prepared from condensation reaction of maleic anhydride with p-chloroaniline. New synthesized organometallic chelates of the proposed general formula [M(CO)4L], where M = Cr, Mo or W, were prepared by reaction of metal hexa carbonyls condensation with bidentate maleanilic acid ligand in inert nitrogen atmosphere. The prepared novel ligand and its organometallic chelates were characterized by elemental analyses, FT-IR, mass spectra, 1H-NMR, and thermal analyses. The results obtained refer to an octahedral structure of the prepared organometallic chelates. The free ligand and its chromium chelate were screened for antitumor activity in vitro against cell lines of HCT-116 (human colon carcinoma), hepG-2 (human hepatocellular carcinoma), and MCF-7 (human breast carcinoma). The results obtained referred to a high antitumor activity of both novel ligand and its chromium chelate.

Acceptorless Dehydrogenative Coupling of Neat Alcohols Using Group VI Sulfide Catalysts

Group VI sulfides were synthesized via coprecipitation of elemental sulfur and metal hexacarbonyl and characterized with XRD, XPS, and TEM. These materials were then demonstrated as active catalysts for the acceptorless dehydrogenative coupling of neat ethanol to ethyl acetate, rapidly reaching equilibrium conversion and up to 90% selectivity. Other primary alcohols form the corresponding esters, while diols formed the corresponding cyclic ethers and oligomers.

Anisotropic Coulomb Explosion of CO Ligands in Group 6 Metal Hexacarbonyls: Cr(CO)6, Mo(CO)6, W(CO)6

Multiple ionization and subsequent Coulomb explosion have been studied for many organic molecules and their clusters; however, the metal complexes, particularly the large Coulombic interactions expected between a metal and its ligands, have not yet been explored. In this study, the angular distribution of CO(+), oxygen, and carbon ions ejected from metal hexacarbonyls (M(CO)6, M: Cr, Mo, W) having Oh symmetry by Coulomb explosion in femtosecond laser fields (>1 × 10(14) W cm(-2)) is investigated. The emissions of oxygen ions are well-explained in terms of the geometric alignment along a line inclined 45° relative to the CO-M-CO axis in a M(CO)4 plane. Unlike the explosion behavior of the oxygen ions located on the outer part of the molecule, the explosion behavior of the carbon ions was affected by the laser intensity, kinetic energy, and metal. This finding that the emission trends of carbon sandwiched between oxygen and metal atoms were the opposite of those for oxygen was explained by the obstruction by oxygen, the deformation of structure in bending coordinates, and the strong interaction with charged metal. The anisotropic Coulomb explosion of metal complexes reflecting their structural symmetry and central metal charge is a promising candidate for use in the investigation of large Coulombic interactions at the molecular level.

Carbon Nanotubes as Electrically Active Nanoreactors for Multi-Step Inorganic Synthesis: Sequential Transformations of Molecules to Nanoclusters and Nanoclusters to Nanoribbons.

In organic synthesis, the composition and structure of products are predetermined by the reaction conditions; however, the synthesis of well-defined inorganic nanostructures often presents a significant challenge yielding nonstoichiometric or polymorphic products. In this study, confinement in the nanoscale cavities of single-walled carbon nanotubes (SWNTs) provides a new approach for multistep inorganic synthesis where sequential chemical transformations take place within the same nanotube. In the first step, SWNTs donate electrons to reactant iodine molecules (I2), transforming them to iodide anions (I(-)). These then react with metal hexacarbonyls (M(CO)6, M = Mo or W) in the next step, yielding anionic nanoclusters [M6I14](2-), the size and composition of which are strictly dictated by the nanotube cavity, as demonstrated by aberration-corrected high resolution transmission electron microscopy, scanning transmission electron microscopy, and energy dispersive X-ray spectroscopy. Atoms in the nanoclusters [M6I14](2-) are arranged in a perfect octahedral geometry and can engage in further chemical reactions within the nanotube, either reacting with each other leading to a new polymeric phase of molybdenum iodide [Mo6I12]n or with hydrogen sulfide gas giving rise to nanoribbons of molybdenum/tungsten disulfide [MS2]n in the third step of the synthesis. Electron microscopy measurements demonstrate that the products of the multistep inorganic transformations are precisely controlled by the SWNT nanoreactor with complementary Raman spectroscopy revealing the remarkable property of SWNTs to act as a reservoir of electrons during the chemical transformation. The electron transfer from the host nanotube to the reacting guest molecules is essential for stabilizing the anionic metal iodide nanoclusters and for their further transformation to metal disulfide nanoribbons synthesized in the nanotubes in high yield.

Decomposition studies of group 6 hexacarbonyl complexes. Part 2: Modelling of the decomposition process

AbstractThe decomposition behavior of group 6 metal hexacarbonyl complexes (M(CO)6) in a tubular flow reactor is simulated. A microscopic Monte-Carlo based model is presented for assessing the first bond dissociation enthalpy of M(CO)6complexes. The suggested approach superimposes a microscopic model of gas adsorption chromatography with a first-order heterogeneous decomposition model. The experimental data on the decomposition of Mo(CO)6and W(CO)6are successfully simulated by introducing available thermodynamic data. Thermodynamic data predicted by relativistic density functional theory is used in our model to deduce the most probable experimental behavior of the corresponding Sg carbonyl complex. Thus, the design of a chemical experiment with Sg(CO)6is suggested, which is sensitive to benchmark our theoretical understanding of the bond stability in carbonyl compounds of the heaviest elements.

Photocatalytic properties of free and oxide-supported MoS2 and WS2 nanoparticles synthesized without surfactants

MoS2 and WS2 are narrow bandgap semiconductors that become photocatalytically active when dispersed on the nanometer scale. Surfactant-free nanoparticles of MoS2 and WS2 were synthesized by thermally decomposing the metal hexacarbonyls in the presence of co-dissolved sulfur. The nanoparticles exhibit a size-dependent shift in their threshold UV–visible absorption. A significant fraction of the nanoparticles is 10–20 nm in diameter. Free unsupported MoS2 and WS2 nanoparticles catalyzed the photodegradation of acetone in an aqueous solution under visible light of wavelength ≥ 400 nm. These nanoparticles did not disperse in the solutions due to hydrophobicity. Water dispersible MoS2 and WS2 were prepared by synthesizing them in the presence of high surface silica or titania (anatase) to produce oxide-supported nanoparticles (1 wt%). These silica- and titania-supported MoS2 and WS2 nanoparticles catalyzed the photodegradation of methylene blue under irradiation of wavelength ≥ 400 nm.

Electron momentum spectroscopy of metal carbonyls: a reinvestigation of the role of nuclear dynamics

The main purpose of this work is to reinvestigate the influence of nuclear dynamics in the electronic ground state of group 6 metal hexacarbonyl compounds [W(CO)6, Cr(CO)6, Mo(CO)6] on electron momentum density profiles obtained from experimental orbital reconstructions employing Electron Momentum Spectroscopy. We call into question the view (Liu et al. in Chem Phys Lett 497:229, 2010) that thermally induced nuclear displacements associated with the first three triply degenerate 1T2g, 1T1u, and 1T2u vibrational eigenmodes can be large enough at or near room temperature (298–310 K) to explain on their own the unexpectedly large electron densities inferred for the frontier orbitals of these compounds at low momenta. In this purpose, we resort to an analysis of populations over these three vibrational eigenmodes, according to a description of vibrational excitations employing Maxwell–Boltzmann statistical thermodynamics. Comparison is made with Born–Oppenheimer Molecular Dynamical (BOMD) simulations over the potential energy surface associated with the electronic ground state. The role of nuclear dynamics in the final ionized state, in the form of Jahn–Teller distortions, is also tentatively investigated.

Functionalization of CPO-27-Ni through metal hexacarbonyls: The role of open Ni2+ sites

Cr(CO)6 and Mo(CO)6 have been used as precursors to obtain grafted (η6-arene) M(CO)3 species inside the CPO-27-Ni material. The presence of open Ni(II) sites in the MOF scaffold promotes distinctive reactivities with respect to that observed previously on other MOFs (MOF-5 and UiO-66). The formation of two organometallic M(CO)3(η6-arene) conformers (staggered and eclipsed) has been considered, also taking into account data obtained by a recent theoretical work. IR spectroscopy shows how open metal sites in a MOF structure can destabilize metal carbonyl molecules, favoring CO elimination and acting as CO scavenger, which fastens the decomposition and frustrate the reverse reaction. The work can open new studies on precursors of catalytic species stabilized inside MOFs cages.